The following reference, which are referred to for their disclosures at various points in this application, are incorporated herein by reference.
J. Amer. Chem. Soc. 45, 521(1923) Japanese Patent Provisional Publication Nos. 138800/76; 124097/77. PA1 J. Org. Syn. Chem., Japan, 41, 972(1983). PA1 J. Poly. Sci., Pt A-1, 10, 2061(1972). PA1 J. Colloid Interface Sci. 47, 705(1974). PA1 Makromol. Chem., 175 699(1974). PA1 J. Phys. Chem., 79, 2254(1975). PA1 Thin Solid Films, 68, 1(1980). PA1 Makromol. Chem., 180, 1059(1979). PA1 "Interfacial Synthesis, Vol. III, Recent Advances," Marcel Dekker: New York, 1981. PA1 J. Macromol. Sci. - Chem., A15, 999(1981). PA1 Makromol. Chem., Rapid Commun., 3, 167(1982). PA1 Macromolecules, 11, 1221(1221). PA1 "Hakumaku (Thin Films)," in "Shin Jikken Kagaku Koza, 18, Kaimen to Colloid (Interfaces and Cooloids)," Maruzen: Tokyo, 1975; Chap. 6, pp. 439-516. PA1 A. W. Adamson, "Physical Chemistry of Surfaces," 4th ed.; Wiley: New York, 1982; Chap. IV. PA1 G. L. Gains, Jr., "Insolbule Monolayers at the Air/Water Interfaces,"; Wiley: New York, 1966; Chap. 4. PA1 Goldfinger, "Clean Surfaces: Their Preparation and Characterization for Interfacial Studies", Marcel Dekker: New York, 1970.
While polymeric imines, even wholly aromatic polymeric imines, and films made therefrom are known to the art, uniform, well-controlled films of less than 0.1 micrometers in thickness have not been heretofore produced. This prior inability to realize such films is due to inherent limitations of the until now state-of-the-art spin coating and vapor deposition processes.
Melt phase and solution phase syntheses of polymeric imines has been known to the art for many years, an early polycondensation synthesis of poly(p-phenylene terephthalaldimine) being that of R. Adams, J. E. Bullock, and W. C. Wilson [Journal of the American Chemical Society, vol. 45, p. 521 (1923)]. Representative examples include the solid state polycondensation of P. W. Morgan [Japan Patent Application No. 51-138800(1976)] and the m-cresol solution polycondensation of Suematsu [Japan Patent Application No. 52-124097(1977)]. Polymeric imines are characterized by high melting points and low solubilities [K. Suematsu and J. Takeda, Journal of Synthetic Organic Chemistry, Japan, vol. 41, pp. 972-984 (1983)]. Because of these properties, ultrathin films of polymeric imines have been heretofore unobtainable.
Also, while ultrathin unit layers and monolayer polymers are known to the art, heretofore, not only have these been limited to polymers not possessing the imine moiety in the main chain, but also they have been limited to polymers soluble in spreading solvents or which possess pendant long alkyl side chains. The following references are considered representative of the prior art in the area of polymerized monolayers and multilayers: R. Ackermann, et al, Kolloid-Z. Z. Polym., vol. 2249, 1118 (1971), A Cemel, et al, J. Polym. Sci., Pt A-1, Vol. 10, 2061 (1972), M. Puterman, et al., J. Colloid Interface Sci., Vol 47, 705 (1974), R. Ackermann, et al, Makromol. Chem., Vol. 175, 699 (1974), A. Dubault, et al, J. Phys. Chem., Vol. 79, 2254 (1975), Banerjee, and J. Lando, Thin Solid Films, Vol. 68, 1 (1980), D. R. Day, and H. Ringsdorf, Makromol. Chem., 180, 1059 (1979), B. Tieke, V. Enkelmann, H. Kapp, G. Lieser, and G. Wegner in "Interfacial Synthesis, Vol. III, Recent Advances," Marcel Dekker: New York, 1981, K. Fukuda, Y. Shibasaki, H. Nakahara, J. Macromol. Sci.-Chem., Vol. A15, 999 (1981), and T. Folda, L. Gross, H. Ringsdorf, Makromol. Chem., Rapid Commun., Vol. 3, 167 (1982).
Amine-aldehyde condensation by grafting an aliphatic aldehyde onto a water-soluble polylysine was proposed by S. J. Valenty [Macromolecules, 11, 1221 (1978)], but the proposed graft polymers were not isolated, and neither substrate-deposited unit layers nor built-up multilayers were obtained. The imino bonds were to occur as side chains on a preformed polymer.
As mentioned above, uniform ultrathin films comprising a polymeric imine which has imino-bonds in the main chain were not heretofore obtained. Ultrathin films comprising a polymer which is not soluble in spreading solvents and which has no long alkyl side chains were also not obtained. Furthermore, unit layer and built-up multilayer films of wholly aromatic polymers have not heretofore been obtained.